As a part of a project of clarifying the physical properties and dynamics of cyanobiphenyls with chiral molecules, thermodynamic properties of (S)-4-(2-methylbutyl)-4'-cyanobiphenyl (5*CB) were investigated by adiabatic calorimetry between T = (5 and 350) K. The complicated phase behaviour was solved and the thermodynamic functions were determined. A new glass transition was identified in the phase II (metastable crystal) at T = 105 K. No inversion of the stability between two crystalline phases was found, being contrary to the expectations from the previous neutron scattering studies. (C) 2008 Elsevier Ltd. All rights reserved.